CN104737336A - Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents

Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery Download PDF

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Publication number
CN104737336A
CN104737336A CN201380054630.0A CN201380054630A CN104737336A CN 104737336 A CN104737336 A CN 104737336A CN 201380054630 A CN201380054630 A CN 201380054630A CN 104737336 A CN104737336 A CN 104737336A
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carbon
secondary battery
ion secondary
oxide
lithium
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神头将之
土屋秀介
大关克知
大崎由惠
西田达也
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Priority to CN201910926687.4A priority Critical patent/CN110635124A/en
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A negative electrode material for a lithium ion secondary battery, the material comprising silicon oxide, having a diffraction peak attributed to Si (111) in the X-ray diffraction spectrum, and in which the silicon crystal grain size, calculated from the diffraction peak, is 2.0-8.0nm.

Description

Anode material for lithium-ion secondary battery, lithium ion secondary battery cathode and lithium rechargeable battery
Technical field
The present invention relates to anode material for lithium-ion secondary battery, lithium ion secondary battery cathode and lithium rechargeable battery.
Background technology
Now, the negative material of lithium rechargeable battery mainly uses graphite, but the discharge capacity of known graphite has the theoretical capacity limits of 372mAh/g.In recent years along with the high performance of the mobile devices such as mobile phone, notebook computer, tablet terminal, require to strengthen to the high capacity of lithium rechargeable battery, requirement can realize the negative material of the further high capacity of lithium rechargeable battery.
Therefore, carrying out that theoretical capacity is high, employing can occlusion and release the element of lithium ion (hereinafter also referred to as " element-specific " actively.To the material of this element-specific be comprised also referred to as " element-specific body " in addition) the exploitation of negative material.
As above-mentioned element-specific, know and have silicon, tin, lead, aluminium etc.Wherein, compared with the negative material that the Si oxide of one of element-specific body is formed with by other element-specific, there is the advantages such as capacity is high, cheap, processability is good, therefore positive especially to the research of the negative material employing Si oxide.
On the other hand, these element-specific bodies known are when having carried out alloying by charging, and volume expands greatly.Such volumetric expansion can make the miniaturization of element-specific body own, and then the structure of the negative material employing these element-specific bodies also can be destroyed and cause conductivity to be cut off.Therefore, capacity is made significantly to be lowered in order to problem due to cyclic process.
For this problem, such as, disclose a kind of non-aqueous electrolyte secondary cell negative electrode material conductivity silicon complex in Japanese Patent No. 3952180 publication, it is characterized in that, the diffraction maximum belonging to Si (111) is observed in X-ray diffraction, the size of the silicon crystal obtained by Scherrer method based on the half value of its diffracted ray is wide is for 1nm ~ 500nm, and described silicon complex to be coated with the particle surface with the structure being dispersed with silicon crystallite in silicon based compound with carbon and to be formed.
According to the technology of Japanese Patent No. 3952180 publication, by by silicon crystallite or microparticulate in nonactive and firm material such as silicon dioxide, further fusion is used for the carbon giving conductivity at least partially to its surface, thus the conductivity forming surface is self-evident, relative to the adjoint occlusion of lithium and the change in volume also stable structure of releasing, as a result, long-time stability and initial efficiency can be improved.
In addition, a kind of negative electrode material for nonaqueous electrode secondary battery is disclosed in Japanese Patent No. 4171897 publication, it is characterized in that, it is for can occlusion and release the electroconductive powder of material surface of lithium ion with graphite coating film, and graphite amount of coating is 3 ~ 40 % by weight, BET specific surface area is 2 ~ 30m 2/ g, this graphite epithelium is 1330cm according to Raman spectrum in Raman shift -1and 1580cm -1near there is the distinctive spectrum of graphite-structure.
According to the technology of Japanese Patent No. 4171897 publication, by by overlayed on can occlusion, release the physical characteristics control of graphite epithelium of material surface of lithium ion in particular range, the negative pole of the lithium rechargeable battery of the characteristic levels that can reach city's site requirements can be obtained.
In addition, disclose a kind of negative electrode material for nonaqueous electrode secondary battery in Japanese Unexamined Patent Publication 2011-90869 publication, it is using the negative material used in the negative pole of the secondary cell of nonaqueous electrolyte, and it is characterized in that, this negative material is at general formula SiO xthe surface of represented Si oxide is coated with the material of carbon epithelium, and above-mentioned carbon epithelium carries out hot plasma process.
According to the technology of Japanese Unexamined Patent Publication 2011-90869 publication, can be resolved as the electrode expansion of silica shortcoming and produce the cell expansion caused because of gas, and cycle characteristics excellence be used as the effective negative material of non-aqueous electrolyte secondary cell negative electrode.
Summary of the invention
The problem that invention will solve
But, when using as one of element-specific body Si oxide be used as negative material, because the efficiency for charge-discharge at initial stage is low, the battery capacity of positive pole must be made excessive when being applicable to actual battery, even if in therefore former technology, in the lithium rechargeable battery of reality, effectively can not utilize the high capacitance features of Si oxide cmpletely.In addition, as the negative material of lithium rechargeable battery of high performance being applicable to applicable mobile device etc. later, must can not only store a large amount of lithium ions (that is, charging capacity is high), the lithium ion of storage can also be released more.Therefore, improve the negative material of contributing as to the further performance of lithium rechargeable battery, the raising taking into account the raising of the discharge capacity at initial stage and the efficiency for charge-discharge at initial stage is very important.
According to a form of the present invention, be the invention completed in view of above-mentioned requirements, problem is to provide the anode material for lithium-ion secondary battery of the discharge capacity at a kind of initial stage and the efficiency for charge-discharge excellence at initial stage, lithium ion secondary battery cathode and lithium rechargeable battery.
The method of dealing with problems
The further investigations such as the present inventor, found that: in order to solve the problem, and following anode material for lithium-ion secondary battery is effective, thus completes the present invention.Form of the present invention is as described below.
< 1 > anode material for lithium-ion secondary battery, it comprises Si oxide, there is the diffraction maximum belonging to Si (111) in X-ray diffraction spectrum, and the size of the silicon crystallite calculated by above-mentioned diffraction maximum is 2.0nm ~ 8.0nm.
Anode material for lithium-ion secondary battery described in < 2 > above-mentioned < 1 >, has carbon further on the part surface of above-mentioned Si oxide or all surfaces.
Anode material for lithium-ion secondary battery described in < 3 > above-mentioned < 2 >, the containing ratio of above-mentioned carbon is more than or equal to 0.5 quality % and is less than 5.0 quality %.
Anode material for lithium-ion secondary battery described in the above-mentioned < 2 of < 4 > > or < 3 >, above-mentioned carbon is low-crystalline carbon.
< 5 > lithium ion secondary battery cathode, it has collector body and is arranged on the negative electrode material layer on above-mentioned collector body, and described negative electrode material layer comprises the anode material for lithium-ion secondary battery in above-mentioned < 1 > ~ < 4 > described in wantonly 1.
< 6 > lithium rechargeable battery, it has positive pole, lithium ion secondary battery cathode described in above-mentioned < 5 > and electrolyte.
Invention effect
According to the present invention, the anode material for lithium-ion secondary battery of the discharge capacity at a kind of initial stage and the efficiency for charge-discharge excellence at initial stage, lithium ion secondary battery cathode and lithium rechargeable battery can be provided.
Accompanying drawing explanation
Fig. 1 is the summary sectional view representing the example that negative material of the present invention is formed.
Fig. 2 is the summary sectional view representing another example that negative material of the present invention is formed.
Fig. 3 is the summary sectional view representing another example that negative material of the present invention is formed.
Fig. 4 is the summary sectional view representing another example that negative material of the present invention is formed.
Fig. 5 is the summary sectional view representing another example that negative material of the present invention is formed.
Fig. 6 A is the sectional view of a part for the negative material of enlarged drawing 1 ~ Fig. 3, is the figure of a state of carbon 10 state illustrated in negative material.
Fig. 6 B is the sectional view of a part for the negative material of enlarged drawing 1 ~ Fig. 3, is the figure of another state of carbon 10 state illustrated in negative material.
Embodiment
In this manual, " ~ " number range of representing is used to represent to comprise numerical value described in before and after " ~ " respectively as the scope of minimum value and maximum.Further about the amount of composition each in composition, when there is the suitable material of multiple and each composition in the composition, as long as no special explanation, just refer to the total amount of this many kinds of substance existed in the composition.
< anode material for lithium-ion secondary battery >
Anode material for lithium-ion secondary battery of the present invention is (following, also only referred to as " negative material ") comprise Si oxide, there is the diffraction maximum belonging to Si (111) in X-ray diffraction spectrum, and the size of the silicon crystallite calculated by above-mentioned diffraction maximum is 2.0nm ~ 8.0nm.
By there is silicon crystallite in above-mentioned Si oxide, and make the size of this silicon crystallite be specific scope, thus when forming lithium rechargeable battery, the high capacity of initial stage discharge capacity and excellent initial charge/discharge efficiency can be realized.This can think: if the size of such as silicon crystallite is specific scope, then can relax expansion and the contraction of adjoint lithium ion occlusion and releasing, simultaneously the capacity of the Si oxide of per unit volume can be suppressed to reduce, therefore the discharge capacity at initial stage and the efficiency for charge-discharge at initial stage excellence.
(Si oxide)
As long as above-mentioned Si oxide comprises the oxide of element silicon, include, for example silicon monoxide (also referred to as silica), silicon dioxide and sub-silica.They can be used alone one, also can combine multiple use.
In Si oxide, silica and silicon dioxide are usually respectively with silicon monoxide (SiO) and silicon dioxide (SiO 2) form represent, but according to surface state (such as, the existence of oxide scale film), generating state, sometimes with the form of the measured value of contained element (or scaled value) by composition formula SiO x(x is 0<x≤2) represents, in this case also as Si oxide of the present invention.In addition, the value of x can carry out oxygen contained in quantitative Si oxide by using non-active gas melting-non-dispersive type infrared absorption, thus calculates.In addition, in the manufacturing process of negative material of the present invention, at the disproportionated reaction (2SiO → Si+SiO with Si oxide 2) when, sometimes to comprise the state representation of silicon and silicon dioxide (optionally for silica) in chemical reaction, in this case also as Si oxide of the present invention.
In addition, silica such as can by making to heat the mixture of silicon dioxide and metallic silicon and the silicon monoxide gas the generated known sublimed method that cools and separate out and obtaining.In addition, can obtain from market as silica, silicon monoxide, single silica (Silicon Monoxide) etc.
Above-mentioned Si oxide has the structure being dispersed with silicon crystallite in this Si oxide.Due to the state for being dispersed with silicon crystallite in Si oxide, thus in X-ray diffraction spectrum, demonstrate the diffraction maximum belonging to Si (111).
The size of the silicon crystallite contained by above-mentioned Si oxide is 2.0nm ~ 8.0nm.If the size of silicon crystallite is less than 2.0nm, then lithium ion and Si oxide easily react, and have the tendency that fully cannot obtain initial stage discharge capacity.In addition, if the size of silicon crystallite is more than 8.0nm, then silicon crystallite easily local existence in Si oxide, in Si oxide, lithium ion is difficult to diffusion, has the tendency that charge-discharge characteristic reduces.The size of silicon crystallite is more preferably and is more than or equal to 3.0nm, is more preferably more than or equal to 4.0nm.In addition, from the viewpoint of cycle characteristics, the size of silicon crystallite is preferably less than or equal to 6.0nm, is more preferably and is less than or equal to 5.0nm.
The size of the silicon single crystal of size contained by above-mentioned Si oxide of above-mentioned silicon crystallite, is calculated by the diffraction maximum belonging to Si (111) in X-ray diffraction spectrum.Specifically, wide by the half value of the diffraction maximum near 2 θ=28.4 ° belonging to Si (111) using the CuK α line of wavelength 0.154056nm in the X-ray diffraction spectrum of line source, calculate based on Scherrer formula.
In addition, about the existence of state being dispersed with silicon crystallite in Si oxide, except can being confirmed by the existence of the diffraction maximum belonging to Si (111) in X-ray diffraction spectrum, such as when using transmission electron microscope to observe Si oxide, can also be confirmed by the existence observing silicon crystal in unbodied Si oxide.
About the structure being dispersed with silicon crystallite in above-mentioned Si oxide, such as can by suitably adjusting heat treatment temperature in heat treatment described later and heat treatment time makes.
The average grain diameter of above-mentioned Si oxide is not particularly limited.Such as, from the viewpoint of discharge capacity and the cycle characteristics at initial stage, the average grain diameter of above-mentioned Si oxide is preferably 0.1 μm ~ 20 μm, is more preferably 0.5 μm ~ 10 μm.
Above-mentioned average grain diameter is volume-cumulative 50% particle diameter (D50%) of particle size distribution.Below, in the statement of average grain diameter too.The mensuration of average grain diameter can adopt laser diffraction granularity to distribute the known method such as meter.
The above-mentioned manufacture method being dispersed with the Si oxide of silicon crystallite is not particularly limited.Such as, disproportionation can be carried out by heat-treating Si oxide with the temperature range of 700 DEG C ~ 1300 DEG C under inert atmosphere, thus be manufactured in Si oxide the Si oxide being dispersed with silicon crystallite.Generate above-mentioned silicon crystallite from the viewpoint of with desired size, heat treatment temperature is preferably greater than or equal to 800 DEG C, more preferably above 850 DEG C, is more preferably more than or equal to 900 DEG C.In addition, heat treatment temperature is preferably less than or equal to 1200 DEG C, is more preferably and is less than 1150 DEG C, is more preferably less than or equal to 1100 DEG C.
As inert atmosphere, include, for example blanket of nitrogen, argon atmospher etc.In addition, heat treatment time suitably can be selected according to heat treatment temperature etc.About heat treatment time, such as, be preferably 1 hour ~ 10 hours, be more preferably 2 hours ~ 7 hours.
Heat treatment temperature in heat treatment is higher, and heat treatment time is longer in addition, has the tendency that the size of silicon crystallite becomes larger.Therefore, in order to make the size of silicon crystallite be desired scope, preferably select heat treatment temperature and heat treatment time.Such as, when heat treatment time being set to 2 hours ~ 7 hours, heat treatment temperature is preferably greater than 850 DEG C and be less than 1150 DEG C, is more preferably and is more than or equal to 900 DEG C and is less than or equal to 1100 DEG C.
About the above-mentioned heat treated Si oxide of supply, when having prepared the bulk silicon oxide of the square degree size of several cm, preferably carry out in advance pulverizing, classification.Specifically, preferably carry out the once pulverizing and the classification that the Si oxide of bulk are crushed to the size can put in atomizer, then by atomizer, separating twice is carried out to it.About the average grain diameter of the Si oxide obtained by separating twice, according to the size of the last negative material expected, be preferably 0.1 μm ~ 20 μm, be more preferably 0.5 μm ~ 10 μm.
Above-mentioned negative material preferably has carbon further on a part for above-mentioned Si oxide surface or all surfaces.The discharge capacity at initial stage and the efficiency for charge-discharge at initial stage improve further thus.In above-mentioned negative material, the containing ratio of above-mentioned carbon is not particularly limited.When above-mentioned negative material comprises carbon, the containing ratio of above-mentioned carbon preferably in the gross mass of negative material for being more than or equal to 0.5 quality % and being less than 5.0 quality %, be more preferably and be more than or equal to 0.5 quality % and be less than or equal to 4.5 quality %, be more preferably more than or equal to 0.5 quality % and be less than or equal to 4.0 quality %.
Carbon containing ratio (quality criteria) in negative material entirety can be burnt till by high frequency-and infrared analysis obtains.High frequency burn till-infrared analysis in, such as can be suitable for carbon sulphur simultaneously analytical equipment (contract commercial firm of LECO Japan system, CSLS600).
Negative material of the present invention is when a part for Si oxide is surperficial or all surfaces has carbon, and its formation is not particularly limited.Fig. 1 ~ Fig. 4 is the summary sectional view of the constitute example representing negative material of the present invention.In FIG, carbon 10 is coated to the whole surface of Si oxide 20.In fig. 2, carbon 10 is coated to the whole surface of Si oxide 20, but does not cover equably.In addition, in figure 3, carbon 10 Si oxide 20 surface local exist, Si oxide 20 surface some expose.In the diagram, the particle had than the Si oxide 20 more carbon 10 of small particle diameter is there is on the surface of Si oxide 20.Fig. 5 is the variation of Fig. 4, and the shape of particle of carbon 10 is flakey.In addition, in Fig. 1 ~ Fig. 5, the shape of Si oxide 20 is schematically represented as spherical (cross sectional shape is circle), but can be also any one in polygonal shape (having the shape at angle) etc. for spherical, block, flakey, cross sectional shape.
Fig. 6 A and Fig. 6 B is a sectional view part for the negative material of Fig. 1 ~ Fig. 3 amplified, and Fig. 6 A illustrates a form of the shape of carbon 10 in negative material, and Fig. 6 B illustrates another form of the shape of carbon 10 in negative material.When Fig. 1 ~ Fig. 3, carbon 10 entirety can be made up of carbon as shown in Figure 6A, also can be made up of particulate 12 by carbon 10 as shown in Figure 6B.In addition, to have remained the state representation of the contour shape of particulate 12 in carbon 10 in Fig. 6 B, but particulate 12 each other also can be in conjunction with.When particulate 12 is bonded to each other, carbon 10 entirety is made up of carbon sometimes, sometimes in a part for carbon 10, comprises space.Space can be comprised like this in a part for carbon 10.
In addition, when carbon 10 is shape of particle, can as shown in Figure 4 carbon 10 particle Si oxide 20 surface local exist, Si oxide 20 surface some expose, also can as shown in Figure 6B carbon 10 particle Si oxide 20 whole surface exist.
When above-mentioned negative material comprises carbon, above-mentioned carbon is preferably low-crystalline carbon.Above-mentioned carbon is that low-crystalline carbon refers to that the following R value in the Raman spectrum of carbon is more than or equal to 0.5.
About the R value in the Raman spectrum of carbon, in the Raman spectrum analysis of argon laser employing wavelength 532nm, 1360cm will be appeared at -1neighbouring peak intensity is designated as I d, will 1580cm be appeared at -1neighbouring peak intensity is designated as I g, by the strength ratio I at this two peak d/ I gwhen (being also designated as D/G) is designated as R value, is preferably greater than or equal to 0.5 and is less than or equal to 1.5, being more preferably and being more than or equal to 0.7 and being less than or equal to 1.3, be more preferably more than or equal to 0.8 and be less than or equal to 1.2.If R value is more than or equal to 0.5, then there is the tendency that can obtain larger charging capacity.In addition, if R value is less than or equal to 1.5, then the tendency that irreversible capacity can be suppressed to increase is had.
Here, 1360cm is appeared at -1neighbouring peak typically refers to and is accredited as the peak corresponding with the amorphous structure of carbon, such as, be at 1300cm -1~ 1400cm -1the peak observed.In addition, 1580cm is appeared at -1neighbouring peak typically refers to and is accredited as the peak corresponding with crystal structure of graphite, such as, be at 1530cm -1~ 1630cm -1the peak observed.
In addition, about R value, raman spectroscopy device (such as, Japanese light splitting (strain) NSR-1000 type (trade name) processed, excitation wavelength 532nm) can be used, for measurement range (830cm -1~ 1940cm -1) with 1050cm -1~ 1750cm -1for baseline is obtained.
As the method for the surface of Si oxide being given to carbon, be not particularly limited, the methods such as wet-mix process, dry-mix process, chemical vapor deposition method can be enumerated.Easily control reaction system from easy mixing and the vpg connection of negative material can be maintained, preferred wet-mix process or dry-mix process.
When wet-mix process, such as can by Si oxide and the solution mixing being dissolved with carbon source in a solvent, the solution of carbon source is made to be attached to silicon oxide surface, as required solvent is removed, heat-treat under inert atmosphere afterwards, thus make carbon source carbonization and give carbon to silicon oxide surface.In addition, under carbon source is not dissolved in the medium situation of solvent, also can be used in dispersant the dispersion liquid being dispersed with carbon source and replaces the above-mentioned solution being dissolved with carbon source in a solvent.
When dry-mix process, such as, Si oxide and carbon source can be made mixture with solids mixing each other, under inert atmosphere, this mixture be heat-treated, thus make carbon source carbonization and give carbon to silicon oxide surface.In addition, when mixing Si oxide and carbon source, also can carry out the process (such as, mechanochemistry process etc.) applying mechanical energy.
When chemical vapor deposition method, known method can be suitable for, such as, can heat-treat Si oxide in the atmosphere comprising the gas making carbon source gasification gained, thus give carbon to the surface of Si oxide.
When giving carbon by said method to the surface of Si oxide, be not particularly limited as above-mentioned carbon source, as long as can carbon compound be remained by heat treatment.Specifically, the macromolecular compounds such as phenolic resins, styrene resin, polyvinyl alcohol, polyvinyl chloride, polyvinyl acetate, polybutyral (polybutyral) can be enumerated; Ethene heavy ends pitch (ethylene heavy end pitch), carbobitumen, petroleum asphalt, coal tar asphalt, pitch cracking pitch, the PVC pitch thermal decompositions such as polyvinyl chloride generated, under super acids exists, naphthalene is made to be polymerized and the pitch class such as naphthalene pitch that makes; The polysaccharide such as starch, cellulose; Deng.These carbon sources can be used alone a kind or combine two or more use.
When giving carbon by chemical vapor deposition method, preferably use gas shape in aliphatic hydrocarbon, aromatic hydrocarbon, clicyclic hydrocarbon etc. or the compound that can easily aerify as carbon source.Specifically, methane, ethane, propane, toluene, benzene, dimethylbenzene, styrene, naphthalene, cresols, anthracene, their derivative etc. can be enumerated.These carbon sources can be used alone a kind or combine two or more use.
As long as be just not particularly limited for the temperature of the heat treatment temperature carbon source carbonization by carbon source carbonization.Heat treatment temperature is preferably greater than or equal to 700 DEG C, is more preferably and is more than or equal to 800 DEG C, further preferably greater than 850 DEG C, is particularly preferably and is more than or equal to 900 DEG C.In addition, be the viewpoint of low-crystalline from the viewpoint of making carbon and generate above-mentioned silicon crystallite with desired size, heat treatment temperature is preferably less than or equal to 1300 DEG C, is more preferably and is less than or equal to 1200 DEG C, more preferably be less than 1150 DEG C, be particularly preferably and be less than or equal to 1100 DEG C.
Heat treatment time is suitably selected according to the carbon source kind, its imparting amount etc. that use.Heat treatment time is such as preferably 1 hour ~ 10 hours, is more preferably 2 hours ~ 7 hours.
In addition, heat treatment is preferably carried out under the inert atmosphere such as nitrogen, argon.As long as annealing device uses the reaction unit with heating arrangements to be just not particularly limited, can enumerate and continuity method, batch process etc. can be utilized to carry out the heater etc. processed.Specifically, can according to its object suitable selective flow layer reacting furnace, rotary furnace, vertical mobile layer reacting furnace, continuous tunnel furnace, batch furnace etc.
When the heat treatment by carbon source forms above-mentioned carbon, the heat treatment of carbon source can double as the disproportionation process of Si oxide.As the heat-treat condition of this situation, from the viewpoint of obtaining the negative material with desired silicon crystallite size, being preferably at 700 DEG C ~ 1300 DEG C 1 hour ~ 10 hours, being more preferably at 900 DEG C ~ 1100 DEG C 2 hours ~ 7 hours.
There is the situation of each particles aggregate in the heat treatment thing obtained by heat treatment, therefore preferably carries out break process.In addition, pulverization process can be carried out further when desired average grain diameter must be adjusted to.
In addition, as the additive method surface of Si oxide being given to carbon, include, for example the method as the carbon given the surface of Si oxide such as the carbonaceous material such as amorphous carbon, graphite that uses soft carbon, hard carbon.According to the method, also can shown in construction drawing 4 and Fig. 5, carbon 10 is present in the negative material of the shape on Si oxide 20 surface in the form of a particle.As the method using above-mentioned carbonaceous material, above-mentioned wet-mix process or above-mentioned dry-mix process can be applied.
When applying wet-mix process, by the particulate of carbonaceous material is mixed with the organic compound (can remain carbon compound by heat treatment) as binding agent and makes mixture, this mixture and Si oxide are mixed further and make mixture be attached to silicon oxide surface, it is heat-treated, thus makes negative material.As above-mentioned organic compound, be just not particularly limited as long as carbon compound can be remained by heat treatment.In addition, the heat-treat condition in application wet-mix process situation, can be suitable for above-mentioned for the heat-treat condition by carbon source carbonization.
When applying dry-mix process, by the particulate of carbonaceous material and Si oxide are made mixture with solids mixing each other, the process (such as, mechanochemistry process) applying mechanical energy is carried out to this mixture, thus make negative material.In addition, when applying dry-mix process, preferably heat-treat to generate silicon crystallite in Si oxide.Heat-treat condition in application dry-mix process situation can be suitable for above-mentioned for the heat-treat condition by carbon source carbonization.
The average grain diameter of the volume reference of above-mentioned negative material is preferably 0.1 μm ~ 20 μm, is more preferably 0.5 μm ~ 10 μm.When average grain diameter is less than or equal to 20 μm, due to the distribution uniformity of the negative material in negative pole, and then expansion during discharge and recharge and shrink homogenizing, therefore there is the tendency that cycle characteristics can be suppressed to reduce.In addition, when average grain diameter is more than or equal to 0.1 μm, negative pole density easily becomes large, has the tendency of easy high capacity.
The specific area of above-mentioned negative material is preferably 0.1m 2/ g ~ 15m 2/ g, is more preferably 0.5m 2/ g ~ 10m 2/ g, more preferably 1.0m 2/ g ~ 7.0m 2/ g.15m is less than or equal in specific area 2when/g, there is the tendency that the first irreversible capacity that can suppress the lithium rechargeable battery of gained increases.Further, the tendency having the use amount that can suppress the binding agent when making negative pole to increase.0.1m is more than or equal in specific area 2when/g, have and increase with the contact area of electrolyte, the tendency that efficiency for charge-discharge improves.About the mensuration of specific area, the method that BET method (nitrogen adsorption methods) etc. is known can be adopted.
In addition, about above-mentioned negative material, the size of preferred silicon crystallite is be more than or equal to 2.0nm and be less than or equal to 8.0nm and containing being more than or equal to 0.5 quality % and being less than the carbon of 5.0 quality %, and more preferably the size of silicon crystallite is be more than or equal to 3.0nm and be less than or equal to 6.0nm and containing being more than or equal to 0.5 quality % and being less than or equal to the carbon of 4.5 quality %.
Negative material can be used with the carbon-based negative electrode material of the known negative electrode active material as lithium rechargeable battery in the past as required.According to the kind of carbon-based negative electrode material also, the expansion suppression etc. of efficiency for charge-discharge raising, cycle characteristics raising, electrode can be obtained.
As carbon-based negative electrode material known in the past, flake natural graphite can be enumerated, by native graphite class, Delanium, amorphous carbons etc. such as the spheroidal natural graphite of flake natural graphite spheroidization.In addition, these carbon-based negative electrode materials can have carbon further at one part surface or all surfaces.Independent one or more of these carbon-based negative electrode materials can be blended in the negative material of the invention described above and use.
When negative material of the present invention and carbon-based negative electrode material are also used and are used, above-mentioned negative material (being designated as SiO-C) of the present invention suitably can adjust according to object with the ratio (SiO-C:C) of carbon-based negative electrode material (being designated as C), such as from the viewpoint of the expansion suppression of electrode, 0.1:99.9 ~ 20:80 is preferably in quality criteria, be more preferably 0.5:99.5 ~ 15:85, more preferably 1:99 ~ 10:90.
< lithium ion secondary battery cathode >
Lithium ion secondary battery cathode of the present invention (below sometimes referred to as " negative pole ") has collector body and is arranged on the negative electrode material layer on above-mentioned collector body, and described negative electrode material layer comprises above-mentioned anode material for lithium-ion secondary battery.Such as, lithium ion secondary battery cathode of the present invention can obtain as follows: coating fluid is modulated in the mixing such as above-mentioned anode material for lithium-ion secondary battery, organic binder bond, solvent or water equal solvent and tackifier as required, conductive auxiliary agent, former known carbon-based negative electrode material, by this coating fluid give (coating) on the current collector after, by above-mentioned solvent or water drying, carry out extrusion forming and form negative electrode material layer.Usually, mixing with organic binder bond and solvent etc. and be shaped to the shape such as sheet, graininess.
Be not particularly limited as above-mentioned organic binder bond, include, for example Styrene-Butadiene; By (methyl) acrylic copolymer that the ethene unsaturated carboxylic acid copolymerization such as ethene esters of unsaturated carboxylic acids and acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylonitrile, (methyl) hydroxy-ethyl acrylate obtain; The macromolecular compounds such as Kynoar, poly(ethylene oxide), Hydrin, polyphosphazene, polyacrylonitrile, polyimides, polyamidoimide.In addition, " (methyl) acrylate " refers to " acrylate " and " methacrylate " corresponding with it.Other similar expression such as " (methyl) acrylic copolymers " too.
These organic binder bonds have dispersion according to respective physical property or are dissolved in the material of gained in water or are dissolved in the material of gained in the organic solvents such as METHYLPYRROLIDONE (NMP).Wherein, from excellent adhesion aspect, preferred main framing is the organic binder bond of polyacrylonitrile, polyimides or polyamidoimide, the excellent aspect of, electrode flexibility low from heat treatment temperature when making negative pole as described later, preferably main framing is the organic binder bond of polyacrylonitrile further.As the organic binder bond taking polyacrylonitrile as main framing, such as, can be used in the product (Hitachi changes into (strain) system, LSR-7 (trade name) etc.) that addition on polyacrylonitrile skeleton has the acrylic acid giving cementability and the straight chain ether giving flexibility.
The ratio that contains of the organic binder bond in the negative electrode layer of ion secondary battery cathode material lithium is preferably 0.1 quality % ~ 20 quality %, is more preferably 0.2 quality % ~ 20 quality %, more preferably 0.3 quality % ~ 15 quality %.
By making the ratio that contains of organic binder bond be more than or equal to 0.1 quality %, adaptation is good, has the tendency that can suppress to cause negative pole destroyed due to expansion during discharge and recharge and contraction.On the other hand, by making the ratio that contains of organic binder bond be less than or equal to 20 quality %, the tendency that electrode resistance can be suppressed to become large is had.
Further, can use as the carboxy methyl cellulose, methylcellulose, CMC, ethyl cellulose, polyvinyl alcohol, polyacrylic acid (ester), oxidized starch, phosphorus oxidation starch, casein etc. that are used for the tackifier adjusting viscosity together with above-mentioned organic binder bond.
Being not particularly limited as the solvent for mixing organic binder bond, 1-METHYLPYRROLIDONE, dimethylacetylamide, dimethyl formamide, gamma-butyrolacton etc. can be used.
In addition, conductive auxiliary agent can be added in above-mentioned coating fluid.As above-mentioned conductive auxiliary agent, include, for example carbon black, acetylene black, the oxide of display conductivity and the nitride etc. of display conductivity.These conductive auxiliary agents can be used alone a kind or combine two or more use.The containing ratio of conductive auxiliary agent is preferably 0.1 quality % ~ 20 quality % in negative electrode material layer (100 quality %).
In addition, be not particularly limited about the material of above-mentioned collector body and shape, as the material of collector body, include, for example aluminium, copper, nickel, titanium, stainless steel, porous metals (foaming metal) and carbon paper.Shape as above-mentioned collector body is not particularly limited, and include, for example foil-like, perforate foil-like and netted.
By above-mentioned coating fluid, (coating) method on the current collector of giving is not particularly limited.As coating process, include, for example metal mask print process, electrostatic coating processes, dip coating, spraying process, rolling method, scrape the known methods such as the skill in using a kitchen knife in cookery, gravure coating process, silk screen print method.Give (coating) and preferably carry out pressurized treatments by platen-press, stack etc. as required afterwards.
In addition, be shaped to the coating fluid of the shape such as sheet, graininess and the integrated of collector body, such as, can be undertaken by the integration utilizing the integration of roller, utilize the integration of press and utilize them to combine.
Be formed in the negative electrode material layer on above-mentioned collector body or the negative electrode material layer integrated with collector body, preferably heat-treat according to the organic binder bond used.Such as, when use take polyacrylonitrile as the organic binder bond of main framing, preferably heat-treat at 100 DEG C ~ 180 DEG C, when the organic binder bond that use is main framing with polyimides or polyamidoimide, preferably heat-treat at 150 DEG C ~ 450 DEG C.
By this heat treatment except desolventizing, solidification organic binder bond carry out high strength, thus the adaptation that can improve between negative material and the adaptation between negative material and collector body.In addition, in order to prevent the oxidation of collector body in process, these heat treatments are preferably carried out under the inert atmosphere such as helium, argon, nitrogen or vacuum atmosphere.
In addition, before heat-treating, negative pole preferably carries out suppressing (pressurized treatments) in advance.Electrode density can be adjusted by carrying out pressurized treatments.In anode material for lithium-ion secondary battery of the present invention, electrode density is preferably 1.4g/cm 3~ 1.9g/cm 3, be more preferably 1.5g/cm 3~ 1.85g/cm 3, more preferably 1.6g/cm 3~ 1.8g/cm 3.About electrode density, its value is higher, more has the tendency that the volume capacity of negative pole improves, and in addition, more has the tendency that the interparticle adaptation of negative material and the adaptation between negative material particle and collector body improve.
< lithium rechargeable battery >
Lithium rechargeable battery of the present invention has positive pole, above-mentioned negative pole and electrolyte.Above-mentioned lithium rechargeable battery can have barrier film as required further.
Above-mentioned negative pole such as relatively can be configured across barrier film and positive pole, and injection comprises electrolyte solution, thus make lithium rechargeable battery.
Above-mentioned positive pole can by forming positive electrode material layer at collector body and obtaining in the same manner as above-mentioned negative pole on the surface.Collector body in above-mentioned positive pole can use the collector body same with the collector body illustrated in above-mentioned negative pole.
About the material used in the positive pole of lithium rechargeable battery of the present invention (also referred to as positive electrode), as long as can adulterate or insert the compound of lithium ion, include, for example cobalt acid lithium (LiCoO 2), lithium nickelate (LiNiO 2) and LiMn2O4 (LiMnO 2).
Positive pole can make as follows: the organic binder bonds such as above-mentioned positive electrode, Kynoar, METHYLPYRROLIDONE, gamma-butyrolacton equal solvent are mixed and modulate positive pole coating fluid, this positive pole coating fluid is given (coating) at least one side of the collector bodies such as aluminium foil, then solvent seasoning is removed, carry out pressurized treatments as required.
In addition, conductive auxiliary agent can be added in above-mentioned positive pole coating fluid.As above-mentioned conductive auxiliary agent, include, for example carbon black, acetylene black, the oxide of display conductivity and the nitride of display conductivity.These conductive auxiliary agents can be used alone a kind or combine two or more use.
The electrolyte used in lithium rechargeable battery of the present invention is not particularly limited, and can use known electrolyte.Such as, electrolytical solution can be dissolved with in organic solvent as electrolyte by using, manufacture nonaqueous lithium ion secondary battery.
As above-mentioned electrolyte, include, for example LiPF 6, LiClO 4, LiBF 4, LiClF 4, LiAsF 6, LiSbF 6, LiAlO 4, LiAlCl 4, LiN (CF 3sO 2) 2, LiN (C 2f 5sO 2) 2, LiC (CF 3sO 2) 3, LiCl, LiI etc.
As above-mentioned organic solvent, as long as above-mentioned electrolyte can be dissolved, include, for example propylene carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, gamma-butyrolacton, 1,2-dimethoxy-ethane and 2-methyltetrahydrofuran.
Above-mentioned barrier film can use known various barrier film.As the object lesson of barrier film, barrier film made of paper, polypropylene barrier film, polyethylene barrier film, glass fibre barrier film etc. can be enumerated.
As the manufacture method of lithium rechargeable battery, such as, first positive pole and negative pole 2 electrodes are reeled across barrier film.The spiral helicine winding group obtained is inserted in battery can, by the lug terminal soldering that welds with the collector body of negative pole in advance at the bottom of battery can.Electrolyte is injected in the battery can of gained, further by the lug terminal soldering that welds with the collector body of positive pole in advance in the lid of battery, across insulating properties pad, lid is configured in the top of battery can, rivets covering the part contacted with battery can and seal, thus obtaining battery.
The form of lithium rechargeable battery of the present invention is not particularly limited, and can enumerate the lithium rechargeable batteries such as paper mold battery, button-type battery, Coin-shaped battery, laminate type battery, cylinder battery, square battery.
About the anode material for lithium-ion secondary battery of the invention described above, describe for lithium rechargeable battery, but go for inserting/depart from all electrochemical appliances that lithium ion is charge-discharge mechanism.
Embodiment
Enumerate synthesis example, embodiment and comparative example below and further illustrate the present invention, but the invention is not restricted to following embodiment.In addition, unless otherwise specified, then " part " and " % " is quality criteria.
[embodiment 1]
(making of negative material)
Use mortar that the block silica (Inc. of (strain) high-purity chemical research institute, specification 10mm ~ 30mm square) as Si oxide is carried out to coarse crushing and obtains silicon oxide particles.After using vibrating mill (small vibrating grinding machine NB-0 (trade name), day Tao Kexue (strain) make) to pulverize further this silicon oxide particles, use the testing sieve of 300M (300 order) to carry out sieve grain, obtain the particulate that average grain diameter is 5 μm.
The mensuration > of < average grain diameter
Sample (5mg) will be measured and put into surfactant (ETHOMEEN T/15 (trade name), Lion (strain) make) the 0.01 quality % aqueous solution, and use oscillating mixer to disperse.The dispersion liquid obtained is put into the sample tank of laser diffraction formula particle size distribution device (SALD3000J (trade name), Inc. of (strain) Shimadzu Seisakusho Ltd.), apply ultrasonic wave while with pump circulation, measure with laser diffraction formula.Condition determination is as described below.Using volume-cumulative 50% particle diameter (D50%) of particle size distribution that obtains as average grain diameter.Below in an embodiment, the mensuration of average grain diameter is similarly carried out.
Light source: red semiconductor laser (690nm)
Absorbance: 0.10 ~ 0.15
Refractive index: 2.00-0.20i
The particulate 970g of the Si oxide obtained and carbobitumen (fixed carbon 50%) 60g is dropped into love to be known in the mixing arrangement (Rocking Mixer RM-10G (trade name)) that motor (strain) is made, after carrying out mixing in 5 minutes, be filled in the heat treatment container of oxidation aluminum.Be filled into after in heat treatment container, in atmosphere firing furnace, under blanket of nitrogen, heat treatment in 900 DEG C, 5 hours carried out to it, obtain heat treatment thing.
Use mortar to carry out fragmentation to the heat treatment thing obtained, sieved by the testing sieve of 300M (300 order), obtain the negative material that average grain diameter is 5.0 μm.
The assay method > of < carbon containing ratio
By high frequency burn till-infrared analysis measures the carbon containing ratio of negative material.High frequency burns till-and infrared analysis is analytical method as described below: in coreless induction furnace, in Oxygen Flow, heating flame carried out to sample, the carbon in sample and sulphur is separately converted to CO 2and SO 2, undertaken quantitatively by infrared absorption.Determinator, s condition determination etc. are as described below.
Device: carbon sulphur is analytical equipment (contract commercial firm of LECO Japan system, CSLS600 (trade name)) simultaneously
Frequency: 18MHz
High frequency output: 1600W
Sample mass: about 0.05g
Analysis time: use automatic mode in the set model of device
Combustion-supporting material: Fe+W/Sn
Standard specimen: Leco501-024 (C:3.03% ± 0.04S:0.055% ± 0.002)
Measure number of times: 2 times (value of the carbon containing ratio in table 1 is the mean value of 2 measured values)
The mensuration > of < R value
Use raman spectroscopy device (Japanese light splitting (strain) NSR-1000 type processed), the spectrum of gained, using following ranges as baseline, carries out the analysis of negative material.Condition determination is as described below.
Optical maser wavelength: 532nm
Exposure intensity: 1.5mW (using the measured value of laser power monitor)
Irradiation time: 60 seconds
Irradiated area: 4 μm 2
Measurement range: 830cm -1~ 1940cm -1
Baseline: 1050cm -1~ 1750cm -1
In addition, about the wave number of the spectrum of gained, the calibration curve using the difference of the wave number theoretical value at the wave number at each peak and each peak of indenes obtained by assay standard material indenes under condition same as described above (with the pure pharmaceutical worker's industry (strain) of light and light one-level) to obtain is revised.
In the profile obtained after correction, 1360cm will be appeared at -1neighbouring peak intensity is designated as I d, will 1580cm be appeared at -1neighbouring peak intensity is designated as I g, obtain the strength ratio I at this two peak d/ I g(D/G) as R value.
The mensuration > of < BET specific surface area
Use high speed specific area/pore distribution measurement device ASAP2020 (MICRO MERITICS system), N2 adsorption under using 5 methods to be determined at liquid nitrogen temperature (77K), by BET method (relative pressure range: 0.05 ~ 0.2) calculate.
The size measurement > of < silicon crystallite
Powder x-ray diffraction determinator (MultiFLex (2kW), (strain) Neo-Confucianism system) is used to carry out the analysis of negative material.The size of silicon crystallite, wide by the half value belonging to the peak of Si (111) crystal face be present near 2 θ=28.4 °, use Scherrer formula to calculate.
Condition determination is as described below.
[condition determination]
Line source: CuK α line (wavelength: 0.154056nm)
Measurement range: 2 θ=10 ° ~ 40 °
Sampling step is wide: 0.02 °
Sweep speed: 1 °/minute
Tube current: 40mA
Tube voltage: 40kV
Divergent slit: 1 °
Scatter slit: 1 °
By optical slits: 0.3mm
In addition, about the profile of gained, use said apparatus incidental structure elucidation software (JADE6, (strain) Neo-Confucianism system) to carry out background (BG) removing with following setting and be separated with peak.
[removing of K α 2 peak and background removing]
K α 1/K α 2 strength ratio: 2.0
BG curve upper and lower (σ) from BG point: 0.0
[appointment at peak]
Belong to the peak of Si (111): 28.4 ° ± 0.3 °
Belong to SiO 2peak: 21 ° ± 0.3 °
[peak separation]
Profile shape function: Pseudo-Voigt
Background is fixed
Read the half value belonging to the peak of Si (111) of being derived from structure elucidation software by above-mentioned setting wide, calculated the size D of silicon crystallite by following Scherrer formula.
D＝Kλ/B cosθ
B＝(B obs 2-b 2) 1/2
D: the size (nm) of crystallite
K:Scherrer constant (0.94)
λ: line source wavelength (0.154056nm)
θ: measure half value broad peak angle
B obs: half value wide (measured value obtained by structure elucidation software)
B: the mensuration half value of standard silicon (Si) is wide
(manufacture method of negative pole)
In powder 3.75 quality % at the negative material made by said method and the Delanium as carbon-based negative electrode material (Hitachi changes into (strain) makes) 71.25 quality % (negative material of making: Delanium=5:95 (mass ratio)), adding relative to the gross mass of above-mentioned powder and adhesive is the LSR-7 as adhesive (Hitachi changes into (strain) system) of the acetylene black as conductive auxiliary agent (electrochemically industry (strain) system) powder of 15 quality %, 10 quality %, mixing afterwards and make slurry.In addition, the addition of adhesive is adjusted to relative to the gross mass of slurry is 10 quality %.Be 10mg/cm with coating weight by this slurry 2mode be coated on the glassy surface of electrolytic copper foil, after predrying 2 hours at 90 DEG C, carry out adjustment by roll squeezer and make density be 1.65g/cm 3.Afterwards, by being cured process in 120 DEG C of dryings 4 hours under vacuum atmosphere, negative pole is obtained.
(making of lithium rechargeable battery)
Use electrode obtained above as negative pole, lithium metal as to electrode, the LiPF comprising 1M 6the mixed liquor of ethylene carbonate/ethyl methyl carbonate (3:7 volume ratio) and ethylene carbonate (VC) (1.0 quality %) as the polyethylene microporous membrane of electrolyte, thickness 25 μm as the copper coin of barrier film, thickness 250 μm as spacer, make 2016 type coin batteries.
(cell evaluation)
< initial discharge capacity, efficiency for charge-discharge >
Battery obtained above is put into the thermostat remaining on 25 DEG C, with 0.43mA (0.32mA/cm 2) carry out constant current charge to 0V after, charge to current attenuation further to the value being equivalent to 0.043mA with 0V constant voltage, measure primary charging capacity.After charging, discharge after inserting the pause of 30 minutes.About electric discharge, with 0.43mA (0.32mA/cm 2) carry out until 1.5V, measure initial discharge capacity.At this moment, capacity conversion becomes the unit mass of negative material used (gross mass by the negative material made and Delanium mix).Calculate the value of initial discharge capacity divided by primary charging capacity gained, as the efficiency for charge-discharge (%) at initial stage.
[embodiment 2 ~ 5]
In the making of the negative material of embodiment 1, except heat treatment temperature being changed to respectively 950 DEG C (embodiments 2), 1000 DEG C (embodiment 3), 1050 DEG C (embodiment 4), 1100 DEG C (embodiment 5), operate similarly to Example 1, make negative material respectively, and carry out same evaluation.
[comparative example 1]
In the making of the negative material of embodiment 1, except heat treatment temperature is changed to except 850 DEG C, operate similarly to Example 1, make negative material, and carry out same evaluation.
In addition, in the negative material that comparative example 1 makes, owing to not observing the diffraction maximum belonging to Si (111), be therefore recited as in Table 1 " ND ".
[comparative example 2]
In the making of the negative material of embodiment 1, except heat treatment temperature is changed to except 1150 DEG C, operate similarly to Example 1, make negative material, and carry out same evaluation.
The evaluation result of above embodiment and comparative example is shown in following table 1.
[table 1]
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
The size [nm] of silicon crystallite 2.0 3.0 4.0 6.0 8.0 ND 11.0
R value (D/G) 1.1 0.9 0.9 1.1 0.9 1.0 1.0
BET specific surface area [m 2/g] 3.7 3.2 2.0 2.2 2.0 4.3 1.9
Average grain diameter [μm] 5.0 5.0 5.0 5.0 5.0 5.0 5.0
Carbon containing ratio [quality %] 3.0 3.0 3.0 3.0 3.0 3.0 3.0
Primary charging capacity [mAh/g] 457 454 450 446 437 466 425
Initial discharge capacity [mAh/g] 407 406 406 402 395 408 385
Efficiency for charge-discharge [%] 89.1 89.4 90.2 90.0 90.4 87.6 90.6
As shown in Table 1: the anode material for lithium-ion secondary battery shown in embodiment 1 ~ 5, the negative material being the comparative example 2 of 11.0nm with the size of the comparative example 1 with silicon crystallite that do not observe silicon crystallite is compared, for initial discharge capacity is large, the negative material of the efficiency for charge-discharge excellence at initial stage.
In addition, be 378mAh/g only used Delanium as primary charging capacity during negative material, initial discharge capacity is 355Ah/g.Result when only used Delanium according to this, in the present embodiment, as negative material, 95 quality % Delaniums are comprised containing 5 quality % negative material of the present invention, even if but negative material of the present invention is such use level, primary charging capacity and initial discharge capacity also improve significantly.
In addition, the disclosure of Japanese publication 2012-237255 is overall by referring to being introduced in this specification.
Whole documents described in this specification, patent application and technical standard, with specifically and describe respectively by referring to and introduce each document, patent application and technical standard situation to same extent, by referring to and introduce in this specification.

Claims (6)

1. an anode material for lithium-ion secondary battery, it comprises Si oxide, has the diffraction maximum belonging to Si (111) in X-ray diffraction spectrum, and the size of the silicon crystallite calculated by described diffraction maximum is 2.0nm ~ 8.0nm.
2. anode material for lithium-ion secondary battery according to claim 1, comprises the carbon of part surface or all surfaces being configured in described Si oxide further.
3. anode material for lithium-ion secondary battery according to claim 2, the containing ratio of described carbon is more than or equal to 0.5 quality % and is less than 5.0 quality %.
4., according to claim 2 or anode material for lithium-ion secondary battery according to claim 3, described carbon is low-crystalline carbon.
5. a lithium ion secondary battery cathode, it has:
Collector body and
Be arranged on the negative electrode material layer on described collector body, described negative electrode material layer comprises the anode material for lithium-ion secondary battery in claim 1 ~ claim 4 described in wantonly 1.
6. a lithium rechargeable battery, it has positive pole, lithium ion secondary battery cathode according to claim 5 and electrolyte.
CN201380054630.0A 2012-10-26 2013-10-25 Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery Pending CN104737336A (en)

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